Aromatic ethebs of l



iatented July 25, 1944 e I UNITED STATES "PATENT OFF-ICE 2,354,032, I

.ssom rrc arm-ms or r,s-BUrsnmNs-on-2 I Arthur Wolfram; Frankiort-on-the-Main, and

Hellmuth Jahn. B'enthen, Upper Silesia, Germany; vested in the Allen Property Custodian No Drawing.

'sp i icaiion July 29, 1941, Serial No. Germany June 6, 1940 4 Claims. (01. 260-012) The present invention relates to aromatic ethers of 1,3-butadiene-oi-2.

We have found that at low temperature there occurs in the presence oi mercury salts an addition of monovinyl acetylene on aromatic hydroxybodies. The aromatic ethers oi 1,3-butadiene- 01-2 are formed according to the equation:

wherein stands ior an aromatic radical.

The constitution oi the product can be established by the fact that upon addition oi dilute sulfuric acid to the compounds obtained, they aresplit into vinyl methylketone and thearomatic hydroxy bodies. Thevinylmethylketone could easily'be detected by its reaction with phenylhydrazine sons to form methyl-3-phenylradicals such as butyl, isobutyl and amyl.

The reaction may also be carried out ln-dilsodium suliate and the ethyl ether is removed.

.iected to steam distillation. The ether layer is separated from the water, the whole is dried over The residue is distilled under reduced pressure. Aiter a slight first running the phenyl ether oi 1,3-butadiene-ol-2 passes over at 65 C. to 66 C. under 3 mm. pressure in t iorm of a colorless oil. The ether is dis ed by an aromatic smell which is not disagreeab e.

(2) A mixture oi 880parts oi m-cresol, 100

, parts oi ethyl ether, 100 parts 0! mercuric oxide and '4 parts oi thiodiphenylamine is cooled to 0- C. and saturated at this temperature with monovinyl acetylene, while vigorously stirring. The product is worked up as described in;Example 1. The m-cresyl ether "oi the 1,3-butadiene-ol-2 passes over under a pressure oi 2 mm. oi mercury at 71 C. to 72 C. in the iorm oi a colorless liquid,-

which likewise has a special smell. The yield amounts to about 1000 parts.

(3) Monovinyl acetylene is introduced'at 0 C. into a mixture oi 500 parts oi meta-chlorophenol, l00 parts oi ethyl ether, 100 parts oi mercuric oxide and 4 parts oi thiodiph'enyl amine, while stirring until the solution is saturated. The reaction product is worked up according to-Example 1 meta-chlorophenyl ether oi 1,3-butadiene- 'olisobtainedwhichundertmmpressurehss uents, for instance in ethers, dioxane, Pyridine or the like. -As' catalyst, mercuric oxide hasi provedito be best; it may be used several times.

- As the new compounds are very polymerizable, it is suitable to work in the presence oi stabilislnl agents, because otherwise part -oi the ethers polymerizes during the iurther treatment. Because oi their polymerizing power the aromatic ethers oi 1,3-butadiene-ol-2 may be used as intermediate products for the preparation oi plastics. I

The iollowing examples serve to illustrate the invention, but they are not iniended'tolimit it thereto, the parts being by weight:

(1) Monovinyl acetylene is introduced in excess at -5 C. toO" C., while stirring, into a mixture or 940 parts oi phenoLBilO parts oi ethyl ether and 70 parts oi mercuric oxide to which there are added 4 parts. oi thiodlphenyl mine as stabilizins agent. The reaction mass is rendered alkaline, while coolins'with ice; and sub- The yields are good. By-products were not ob- 4 served.

a boiling point oi- 81 C. and becomes yellowish whenexposedtoth air. Tbisetherhasalso an aromatic smell.

' We claim:

"1. The process oi producins aromatic ethers oi 1,3-butadiene-ol-2 which comprises reactins monovinyl acetylene upon a phenol at a temperature oi about 0 C. in the presence oi mercurlc oxide as a catalyst.

2. The process-oi producins the phenol ether oi 1,3-butadiene-ol-2 which comprises reactins monovinyl acetylene upon phenol at a temperature oi irom -6 C. to 0' C. in the presence oi mercuric oxide as a catalyst. I

8. The process oi producins the m-cresyl' ether oi 1,3-butadiene-ol-2 which comprises reactins monovinyl acetylene upon m-cresol at a tempersture oi 0 C. in the presence oi mercuric oxide, as a catalyst.

4.,The process oi producing the m-chlorophenol ether oi 1,3-butadiene-ol-2 which comprises reactina monovinyl acetylene upon mchlorophenol at 0' C. in the presence oi mercuric oxide as a catalyst.

' ARTHUR WOII'RAM.

mum's JAHN. 

